Alkyl aryl sulfonate-carboxy-methylcellulose-alkaline salt detergent composition



p 4, 1951 c. E. SMITH EI'AL 2,566,501

ALKYL ARYL SULFONATE-CARBOXYMETHYLCELLULOSE-ALKALINE SALT DETERGENT COMPOSITION Filed Jan. 30. 1948 2 Shooter-Sheet 1 9 'AA FIG. I

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ALKYL ARYL SULF'ONATE-CARBOXYMETHYLCELLULOSE-ALKALINE SALT DETERGENT COMPOSITION Filed Jan. 30, 1948 2 Sheets-Sheet 2 3 I A a 60 MAVAVAVAVA ,fiilvx'i'ivfi i$vivvvv o zvvvvvvvvvy Sodium I Oorboxymoihylcdlulou,

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Clifton 5.5mm E Thomas M. Vaughn INVENTORs BY 2%,, W

Attorney Patented Sept. 4, 1951 ALKYL ARYL SULFONATE-GARBOXY- METHYLCELLULOSE-ALKALINE SALT DETERGENT COMPOSITION Clifton E. Smith, Wyandotte, and Thomas H.

Vaughn, Grouse Ile, Mich., dotte Chemicals Corporation,

assignor to Wyan- Wyandotte,

Mich., a corporation of Michigan Application January 30, 1948, Serial No. 5,334

1 v The present invention relates to a three com- POnent detergent composition which, due to the prescribed balance of proportions of its ingredients, displays a detersive action that is most unusual and unexpected. The tions embodying the principle of our invention have rendered it commercially feasible for the first time to employ synthetic detergent-based compositions in the laundering of cotton fabrics, in which operation it has heretofore been found necessary to employ a soap-based detergent in order to obtain satisfactory results. In the copending U. S. patent application Serial No. 677,034 filed June 15, 1946, by E. F. Hill, C. E. Smith and T. H. Vaughn, said Smith and said Vaughn being the applicants herein, it is taught that the detersive action of a synthetic detergent of the alkyl aryl sulfonate type, such as sodium 'fkeryl" benzene sulfonate, whose alkyl group contains an average of 12 carbon atoms and is derived from a petroleum distillate fraction boiling in the range of 150-300" C. and whose aryl group is derived from an aromatic hydrocarbon of the benzene series, creased by the addition cellulose (also known in chemical nomenclature as sodium cellulose glycollate); and that the presence of inorganic alkaline salts imparts a still greater improvement sodium keryl" benzenesulfonate constituent as disclosed in said copending application may be employedin its salt-free form or in its saltbuilt form (i. e. containing sodium sulfate) without materially affecting or altering its function as a detergent composition ingredient. This is also true in the present case, where either of the two forms of the sodium "keryl" benzenesulfonate are the full functional equivalents of each other.

By thoroughly exploring the ternary system of alkyl aryl sulfonate-carboxymethylcelluloseinorganic alkaline salt, we have now discovered that a proper balance of the proportions of these ingredients, produces an improved detergency which is over 25% better than that of the alkyl aryl sulfonate alone. By the determination of the range proportions of such proper balance of ingredients, we have also discovered that it is possible to formulate commercially desirable and economically feasible synthetic detergent-based compositions which possess a detergency in the detergent composiin detergency. The

can be exceptionally inof sodium carboxymethyl- 8 Claims. (Cl. 252-138) 2 laundering of cotton fabrics which is equal to and greater than that of soap-based compositions. 7 v

Briefly outlined, the compositions of our invention conform to the following range proportions:

The inorganic alkaline salts or "builders, as they have customarily been called in the detergent art, that have been found most suitablefor incorporation in the compositions of our invention are: sodium carbonate, modified soda, (a combination of NazCOa and NaHCOa) sodium metasilicate, and a reaction product of sodium carbonate and sodium silicate (i. e.- a sodium silicate having an NazO/SiO: mol ratio in the water glass range of 1' mol NazO per 2.04.2 mols of SiO:)

To the accomplishment of the foregoing ends and to enable any person skilled in. the art readily to understand and practice the invention. the following full and concise description and annexed drawing set forth the best mode in which we have contemplated applying the principle thereof.

In said annexed drawing coordinate graph, or

Fig. 1 is a triangular ternary diagram, illustrating the proportion ranges of the three basic ingredients of our compositions, wherein the improved deters'ive action values are obtained;

Fig. 2 is a ,ternary'diagram showing the isodetergency value curves for the system sodium keryl benzenesulfonate-sodium carboxymethylcellulose-sodium carbonate;

Fig. 3 is a ternary system diagram similar to that of Fig. 2, but for the three-component system wherein modified soda has been substituted for sodium carbonate; and

Fig. 4 is a ternary component diagram similar to that of Fig. 2, but for a three-ingredient system wherein a sodium carbonate-sodium silicate reaction product has been substituted for sodium carbonate.

As previously indicated, the three-component or three-ingredient system upon which our invention is based was carefully explored by making a large number of formulations in which the proportions of each individual ingredient was varied over the range from to-100% by weight. Such formulations were then tested for deterslve efliciency according to the following procedure:

Soil removal test procedure A standard soiled cotton fabric is first prepared as follows:

Fourteen pieces of a standard muslin ("Indian Head muslin 53 x 47, 5.15 oz. per sq. yd. manufactured by Nashua Mfg. Co.) are definished or pre-treated in order to remove the sizing or finish and to shrink the material, by a. treatment with caustic soda solution, followed by a wash with sodium stearate, which is then followed by a number of rinses with soft water. The water used in this operation is softened to below one grain CaCOi equivalent to a gallon. Following such pre-treating operation, the muslin is extracted for minutes and tumbled to dryness in a commercial gas-heated laundry dryer. The definished standard muslin, cut in pieces measuring x 36" are placed in a Monel metal wash wheel containing an emulsion of colloidal carbon black and water-soluble mineral oil. After thorough impregnation of the standard muslin in the carbon black and oil emulsion, it is removed piece by piece and passed once without folding through a power-driven household type wringer to squeeze out any residual aqueous dispersion, the wringer pressure being so adjusted as to leave in the cloth an amount of standard soil solution equal to 120% i1% of the dry weight of cloth. The standard soiled muslin or test cloth is then dried and ,cut into test pieces measuring 2%" I: 3 Before actual use of the so-prepared standard soiled cloth; it is given a. final check by the following described carbon soil removal test in a standard detergent solution, and over a range of several solution concentrations. To evaluate the soil removal characteristics of synthetic detergent compositions, 0.25% by weight solutions of the composition to be tested are prepared in distilled water and 100 ml. portions of such solution are added to each of '10 onepint jars of a "Launder-O-Meter (type 12Q-EF- SPA, manufactured by Atlas Electric Devices Company) standard laundry test machine.

Fifteen /4' diameter stainless steel balls are placed in each jar, after which two pieces of the previously prepared standard soiled cloth are added to each of nine jars. In the tenth jar are placed two pieces of unsoiied but pre-treated cloth and this latter jar serves as a blank for determining the turbidity of the detergent solution. The so-prepared jars, heated to a temperature of 140- *:2 C. in a constant temperature bath are then placed in the "Launder-O-Meter and run for '10 minutes at a speed of 42:1 R. P. M. The jars are then removed from the test machine and replaced in the constant temperature bath. The contents of each jar to which the standard soil cloth has been added are poured through a coarse screen to separate the steel balls and the standard soiled cloth from the soil suspension which is collected in a large beaker. The composite suspension thus attained is mixed thoroughly and a sample placed in a 10 mm. light absorption cell. The light absorption of this composite solution, as well as the light absorption ofthe solution in the tenth or "blank" jar containing the unsoiled cloth test pieces is then measured (by 8. "Fisher Electrophotometer"). By means of a calibration curve for the Fisher Electrophotometer, such curve being constructed by obtaining light absorption values of known quantities of carbon black dispersion added to distilled water, the carbon soil removal value sought (in mg. per carbon per liter of solution) is obtained by taking the diiference between the converted values of the light absorption of the composite solution or suspension from the nine jars and of the light absorption of the suspension in the blank jar.

The soil removal values are then reported as a percentage of that of a standard detergent solution used as a reference or control material; viz: by dividing the mg. of carbon removal value of the test material composition by the mg. of

carbon removal value for the standard or control detergent solution which is determined concurrently in the same test run and on the same standard soiled test cloth, and multiplying by 100. In the present reported test-results, the standard detergent solution employed was a 0.25% solution of sodium keryl benzenesulfonate (Kreelon, grade 4D, containing on the average 40% by weight organic sulfonate and Na2SO4).

with varying amounts of the three basic ingredients of our detergent compositions, over ranges of 0100% by weight for each ingredient and at increments of 5% variation for each ingredient. The specific ingredients employed in the test formulations were as follows:

1. Alkyl aryl sulfonatc synthetic detergent: a sodium "keryP benzenesulfonate having an alkyl group containing an average of 12 carbon atoms and derived from a petroleum distillate fraction boiling in the range of 150-300 C. and an aryl group derived from benzene. This sodium kcryl" benzenesulfonate was of the "salt-built" type containing 40% by weight of alkyl aryl sulfonate and 60% by weight of NazSOi; and further identified as "Kreelon grade 41').

2. Sodium carboxymethylcellulose: containing. by analysis, 50.8% by weight of sodium carboxymethylcellulose, 15.7 NaCl, and 10.6% moisturei a technical form of sodium carboxymethylcellulose, manufactured by Wyandotte Chemicals Corporation and specifically identified under the trade name Carbose," Lot C-1716A.

3. Inorganic alkaline salts: Sodium carbonate -a commercial grade of soda ash analyzing 99.5 NazCOz; modified soda-a commercial grade having an average mol ratio of NazCQ: to NaHCO: of 1 to 1.39.

The carbon soil removal values for the test formulations were then plotted on a triangular coordinate graph as exemplified by Fig. 1. It was found that in the compositions falling within the area denoted by the triangle A, B and C, that a detergency value amounting to approximately and greater of standard was obtained. Outside of this area ABC, lesser detcrgency values occurred, ranging down to substantially less than 100% of standard.

It was also found that formulations within the triangular area DEF of Fig. 1, rose to a still higher detergency improvement on the order of and greater. In other words. the area DEF represents a still higher "plateau" of detergency improvement, as compared to the area ABC.

' Per cent Sodium "keryl" benzenesulfonate 20-95 Sodium carboxymethylcellulose -80 Inorganic alkaline salt 0-75 and the area DEF corresponds to the following range proportions:

. Per cent Sodium "keryP benzenesulfonate 40-90 Sodium carboxymethylcellulose -60 Inorganic alkaline salt 0-50 Sodium "keryF benzenesulfonate alone (point X), 100% of standard.

Sodium carboxymethylcellulose alone (point Y),

100% of standard.

Sodium carbonate alone (point Z), 44% of standard.

In Fig. 2, curves denoted I25 and I50 have been drawn through the detergeney evaluation points corresponding to 125% and 150%, respectively, for the formulations based on sodium keryP benezenesulfonate, sodium carboxymethylcellulose and sodium carbonate. It will thus be seen from Fig. 2 the manner in which the iso-detergency curve I25 and the iso-detergency curve I50 confirm and support the determination .of the areas ABC and DEF. Thus, the formulations of sodium keryl benzenesulfonate, sodium carboxymethylcellulose and sodium carbonate in the proportions falling within the areas defined in Fig. 2 by the curves I25 and I50 and the XY coordinate, are found to possess detergency values of 125 and 150%, respectively, of standard.

Fig. 3 is a triangular coordinate graph for the specific formulations containing sodium "keryP benzenesulfonate, sodium carboxymethylcellulose and modified soda. In this case it will again be seen wherein the iso-detergency curves I25 and I50 confirm the establishment of the range proportion areas ABC and DEF.

And again, in the case of Fig. 4, it is found that the iso-detergency curves I25 and I50 again present a confirmance of the range proportion areas ABC and DEF in the case of the specific gredients sodium "keryP benzenesulfonate, sodium carboxymethylcellulose and the reaction product of sodium carbonate and sodium silicate.

In the case of Fig. 4 it is interesting to note that an exceptionally high plateau of detergency improvement is obtained within the area delineated by the curve I15. In fact, detergency evaluations of as high as 185% of standard are obtained within this latter area.

When it is considered that the detergency evaluation of a good grade of unbuilt soap of a type commonly used in commercial laundry,

- under identical test conditions, has a carbon soil removal value of 145% of standard, then the unusual detersive action or the compositions of our invention canbe appreciated.

Specific formulations based upon sodium keryl benzenesulfonate, sodium carboxymethylcellulose and sodiu metasilicate, also display the detergent improvement evaluations and range proportion determinations, of the previously described detergent composition formulations. The more commonly available pentahydrate form of sodium metasilicate is preferably employed as the inorganic alkaline salt ingredient. However, the anhydrous form is equally well suitable and produces equivalent results.

In the annexed claims where the term sodium keryl benzenesulfonate tended to include within its scope both the saltfree and Nazsoi-containing forms and. to mean an alkyl aryl sulfonate whose alkyl group contains on the average of 12 carbon atoms and is derived from the petroleum distillate fraction boiling in the range of 150-300 C. and whose aryl group is derived from a hydrocarbon in the benzene series, 1. e. benzene, toluene, xy-

lene, etc.

. described and illustrated in The percentages given for the proportions of ingredients in the appended claims are to be understood as being on the technically dry, solid basis, i. e. as containing only such amounts of moisture, not including water of molecular com-.

bination, as is customarily or technical grades in their solid form.

Other modes of applying the principle of our invention, in addition to the one hereinabove detail, may be employed, provided the elements stated by any of the following claims or the equivalent of such elements be utilized.

We, therefore, particularly point out and distinctly claim as our invention and discovery:

1. A detergent composition consisting essentially of 20-95% by weight of sodium alkyl benzenesulfonate, whose alkyl group contains an average of 12 carbon atoms and is derived from a petroleum distillate fraction boiling in the range of -300 G, 5-80% sodium carboxymethylcellulose, and the balance an alkaline compound selected from the group consisting of sodium carbonate, modified soda, sodium metasilicate and the reaction product of sodium carbonate and sodium silicate having an NazO/SiOz mol ratio of 1 to 2.0-4.2, the maximum amount of said alkaline compound being not over 75%.

2. The composition as in claim 1 wherein the alkaline compound is sodium carbonate.

3. The composition as in claim 1 wherein the alkaline compound is modified soda.

4. The composition as in claim 1 wherein the alkaline compound is the reaction product of sodium carbonate and sodium silicate having an NazO/SiOz mol ratio of l to 2.0-4.2.

5. A detergent composition consisting essentially of 40-90% by weight of sodium alkyl benfound in commercial of the respective ingredients zenesulfonate whose alkyl group contains an average of 12 carbon atoms and is derived from a petroleum distillate fraction boiling in the range of 150-300 C., 10-60% sodium carboxymethylcellulose, and the balance an alkaline compound selected from the group consisting of sodium carbonate, modified soda, sodium metasilicate and the reaction product of sodium carbonate and sodium silicate having an NazO/SiO: mol ratio of 1 to 2.0-4.2, the maximum amount of said alkaline compound being not over 50%.

is employed, it is in- 6. Thmcomposltion as in claim 5 wherein the alkaline compound is sodium carbonate.

7. The composition as in claim 5 wherein the alkaline compound is modified soda.

8 The composition as; in claim 5 wherein the alkaline compound is the reaction product of sodium carbonate and sodium silicate having an Nam/Slog mol ratio of 1 to 2.0-4.2.

a CLIFTON .E. SMITH.

THOMAS H. VAUGHN.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Number Name Date 2,220,099 Guenther et a1 Nov. 5,1940 2,247,365 Flett July 1, 1941 2,335,194 Nuesslein et al NOV, 23, 1943 2,347,336 Sey-terth Apr. 25, 1944 2,404,289 Hicks July 16,1946

OTHER REFERENCES In I Cellulose and Cellulose Derivafiives, Ott. In terscience Pub. Inc., N. Y. (1943) page 787. 

1. A DETERGENT COMPOSITION CONSISTING ESSENTIALLY OF 20-95% BY WEIGHT OF SODIUM ALKYL BENZENESULFONATE, WHOSE ALKYL GROUP CONTAINS AN AVERAGE OF 12 CARBON ATOMS AND IS DERIVED FROM A PETROLEUM DISTILLATE FRACTION BOILING IN THE RANGE OF 150-300* C., 5-80% SODIUM CARBOXYMETHYLCELLULOSE, AND THE BALANCE AN ALKALINE COMPOUND SELECTED FROM THE GROUP CONSISTING OF SODIUM CARBONATE, MODIFIED SODA, SODIUM METASILICATE AND THE REACTION PRODUCT OF SODIUM METABONATE AND SODIUM SILICATE HAVING AN NA2O/SIO2 MOL RATIO OF 1 TO 2.0-4.2, THE MAXIMUM AMOUNT OF SAID ALKALINE COMPOUND BEING NOT OVER 75%, 